JPS5912692B2 - Stabilized synthetic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION 5 The present invention relates to a stabilizer for synthetic resins, and particularly to a novel stabilizer that suppresses high-temperature decomposition of vinyl chloride polymers and copolymers, ABS resins, and the like.

For example, when vinyl chloride resin is heated and molded,
It tends to cause thermal decomposition mainly due to dehydrochlorination, which tends to cause deterioration in mechanical properties and color tone of processed products, which has the drawback of causing significant disadvantages. In order to eliminate such drawbacks, it is necessary to add one or more types of heat stabilizers to the synthetic resin to suppress deterioration during processing steps. Many metal soaps have been used in the prior art for this purpose. However, the thermal stability is still insufficient, and satisfactory results that can withstand practical use have not been obtained. In order to solve these drawbacks associated with conventional stabilizers20, the present inventors have conducted intensive research and have developed a synthetic resin that requires a compound having oxygen and sulfur atoms in the molecule as a stabilizer. It was revealed for the first time that a synthetic resin with excellent stability can be obtained by adding it to

25 The compound used in the present invention has the following general formula (I).

R.

R3 and R4 each represent a hydrogen atom, an alkyl group, or an aryl group.

35X1 and X2 each represent a sulfur atom or an oxygen atom, and the ratio of sulfur atom/oxygen atom in one molecule is 1/2 to
The range is 80.

ιha n represents a number from 5 to 80.

(In addition, when there are the same symbols in one molecule, they may be the same or different.

)] The compound represented by the above general formula is a synthetic resin 100
0.001 to 10 parts by weight, preferably 0
．． 01 to 1.5 parts by weight can be used depending on the purpose.

One or several kinds of plasticizers can be used in the composition of the present invention depending on the purpose, and these include phthalate esters, other esters, polyester plasticizers, phosphate ester plasticizers, chlorine Examples include plasticizers such as epoxy plasticizers, epoxy plasticizers, and other plasticizers.
This is typified by No. 21169.

Adding an antioxidant to the synthetic resin used in the present invention can increase the oxidative deterioration prevention property of the synthetic resin.
It can be used as appropriate depending on the purpose of use.

These antioxidants include phenolic antioxidants, phosphite antioxidants, amine antioxidants, sulfur-containing compounds, etc. Examples of phenolic antioxidants include 1-oxy-3-methyl -4-isopropylbenzene, 2,6-di-tert-butylphenol, 2,4-
Dimethyl-6-1-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-2(2'-methylcyclohexyl)phenol, alkylated phenol, 2,5- Di-tert-butylhydroquinone, 3-tert-butyl-4-oxyanisole, styrenated phenol, hydroquinone monobenzyl ether, 2,5-di-tertiary amyl (hydroquinone,
2,6-di-tert-butyl-4-methoxyphenol, 4
-Hydroxymethyl-2,6-di-tert-butylphenol, 2,6-di-tert-butyl-2-dimethylamino-p
-cresol, 4-oxy-3,5-di-tert-butylbenzylphosphonic acid ester, such as dimethyl, diethyl or dioctadecyl ester, β-4-oxy-3
, 5-di-tert-butylphenylpropionic acid and a monohydric or polyhydric alcohol, such as methanol, ethanol, octadecanol, hexanediol, 4-nonanediol,
Esters with trimethylhexanediol, thiodiethylene glycol, trimethylolethane or pentaerythritol, 6-(4-oxy-3,5-tert-butylanilino)-2,4-dioctyl-thio-S-triazine, 2,4-bis (3,5-di-tert-butyl-4-oxy-phenoxy)-6-octylthio-S-triazine,
N-stearoyl para-aminophenol, 4-4'-dioxydiphenyl, 4,4'-bis-(2,6-di-tert-butylphenol), 2,'2'-methylene-bis-(4- Methyl-6-tert-butylphenol), 2,
Z-methylene-bis-(4-ethyl-6-tert-butylphenol), 4,4'-methylene-bis-(6-tert-butyl-0-cresol), 4,4'-methylene-bis-
(2,6-di-tert-butylphenol), 2,2'-dioxy-3,3'-di(α-methylcyclohexyl)
-5,5'-dimethyl-diphenylmethane, 1,1-bis-(4-oxy-phenyl)-cyclohexane, 4,
4'-cyclohexylidene-bis(2-cyclohexylphenol), 4,4'-butylidene-bis(6-tert-butyl-m-cresol), 2,2'-thio-bis-
(4-methyl-6-tert-butylphenol), bis-(
2-oxy-3,5-di-tert-butylphenol) sulfide, 4,4'-thio-bis-(3-methyl-6-tert-butylphenol), 4,4'-thio-bis-(6- tert-butyl-0-cresol), esters of bis-(3,5-di-tert-butyl-4-oxybenzyl)-malonic acid, such as didodecyl ester, dioctadecyl ester and 2-dodecylmercabutoethyl ester and p-tertiary octylphenyl ester, 1,1-bis(4
-oxy-2-methyl-5-tert-butylphenyl)-3
-dodecylmercapto-butane, 2-(3-methyl-4
-oxy-5-tert-butylbenzyl)-malonic acid dioctadecyl ester, S-(3,5-dimethyl-4-oxyphenyl)-thioglycolic acid octadecyl ester, tris-(3,5-di-tert-butyl-4 -oxybenzyl)isocyanurate, 2,6-bis-(2'-oxy-3'-tert-butyl-5'-methylbenzyl)-4-
Methylphenol, 1,1,3-tris-(2'-methyl-4'-oxy-5'-tert-butylphenyl)-butane, 1,3,5-tris-(3',5'-di-tert-butylphenyl)-butane, 3-butyl-4'-oxybenzyl)-2,4,6-trimethylbenzene, tris(3,5-di-tert-butyl-4-oxyphenyl)phosphate, 4-oxymethyl-1-bosphor2,6,7 -Trioxapin glow [2,2,
2]-Octane-3-(3,5-di-tert-butyl-4-oxyphenyl)-propionate, 1,3,5-tris(3,5-di-tert-butyl-4-oxyhydrocinnamoyl)hexahy 5 Draw S-Triazine, Tris (
Examples of the phosphite-based antioxidants include 3,5-di-tert-butyl-4-oxyphenylpropionyloxyethyl) isocyanurate, diphenyldecyl phosphite, triphenyl phosphite, and tris-1-nonyl phenyl phosphite. , tridecyl phosphite, tris(2-ethylhexyl) phosphite, tributyl phosphite, dilauryl acid phosphite, dibutyl acid phosphite, tris(dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis(neopentyl) glycol)
1,4 cyclohexane dimethylene phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, diphenyl acid phosphite, tris (lauryl-2-thioethyl) phosphite, tris (monodi mixed nonylphenyl) phosphite, hydrogenated -4,4'-isopropylidene diphenol polyphosphite, diphenyl bis[
4,4/-n-butylidene bis(2-tert-butyl-5-
methylphenol)]thiodiethanol diphosphite, bis(octylphenol(ha) bis[4,4'-n
-Butylidene bis(2-tert-butyl-5-methylphenol)] 1,6 hexanediol diphosphite, phenyl 4,4'-isopropylidene diphenol pentaerythritol diphosphite, phenyl diisodecyl phosphite, tetratri Decyl-4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol) diphosphite, tetratridecyl-1,1,3-tris(2'-methyl-5-tert-butyl-4'- oxyphenyl)butane diphosphite, tetra(C,2-15
mixed alkyl) 4,4'-isopropylidene diphenyl diphosphite, tris(4-oxy-2,5-ditertiary
Butylpheno(ha)phosphite, tris(4-oxy-3,5-di-tert-butylphenyl)phosphite,
2-ethylhexyl diphenyl phosphite, examples of amine antioxidants include phenyl-1-naphthylamine, phenyl-2-naphthylamine, N,N/-diphenyl-p-phenylenediamine, N,N'-di-2 −
Naphthyl-p-phenylenediamine, N,N/-di-sec-butyl-p-phenylenediamine, 6-ethoxy-2
,2,4-trimethyl-1,2-dihydroquinoline, 6
-Dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, mono- and dioctyliminodibenzyl, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline, sulfur-based antioxidants, For example, esters of β-thiodipropionic acid, such as ethyl, lauryl,
Stearyl, myristyl or tridecyl ester, 2
- salts of mercaptobenzimidazole, such as zinc salts, diphenylthiourea, stearyl mono(3,5-dimethyl-4-oxybenzyl)thioglycolic acid ester,
Thiodipropionic acid, phenothiazine, tetra-scratch (β
-dodecylthiopropionyloxymethyl)methane. By adding an ultraviolet absorber to the synthetic resin used in the present invention, the photostability can be improved, so it is also possible to select and use this as appropriate depending on the purpose of use.

These include benzophenones, benzotriazoles, succinates, substituted acrylonitriles, various metal salts or chelates, especially nickel, manganese or chromium salts or chelates, triazines, oxalamides, piperidines, etc. Included. In addition, as necessary, for example, metal soap epoxy stabilizers, organic chelates, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants,
Fluorescent agents, antifungal agents, bactericidal agents, metal deactivators, photodegradants,
Nonmetallic stabilizers, epoxy resins, boric acid esters, thiourea derivatives, nucleating agents, clarifying processing aids, mold release agents, and the like can also be included. In general, metal soaps can be used as stabilizers for synthetic resins. Metal soaps such as , strontium, sodium, and potassium are often used in combination of two or more of these; for example, Cd-BalCd-Ba-Z
nlBa-ZnsCa-ZnsCa-MglCa-Mg
-ZnsCd-Ba-organotin, Cd-Ba-PbsCa
Many combinations such as -SrsZn-NalZn-K are adopted depending on the purpose of use.

In the synthetic resin composition of the present invention, a combination of metal soaps or a single metal soap can be used depending on the purpose from among the many metal soap groups commonly used.
Examples of the synthetic resin composition used in the present invention include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, and chlorinated polyethylene. Vinyl monoacetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride monovinylidene chloride copolymer, chloride Vinyl-styrene monomaleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride monochlorinated propylene copolymer, chloride Vinyl monochloride vinylidene monoacetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-
Halogen-containing synthetic resins such as methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, internally plasticized polyvinyl chloride, α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-3-methylbutene, or ethylene monoacetic acid Polyolefins such as vinyl copolymers, ethylene-propylene copolymers and their copolymers, polystyrene, polyvinyl acetate, acrylic resins, combinations of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.) copolymer, acrylonitrile-butadiene-styrene copolymer,
Acrylic ester-butadiene-styrene copolymer,
Methacrylic acid ester-butadiene-styrene copolymers or blends of these resins, block copolymers, graft copolymers, polyoxyphenylene polymers, polyoxymethylene polymers, polyethylene oxide, polypropylene oxide polymers, Examples include epichlorohydrin polymers, epichlorohydrin-ethylene oxide copolymers, epoxy resins, polyester resins, and polyvinyl butyral resins. In the present invention, preferred examples of the compounds represented by the above general formula are shown in Table 1 below as average formulas.

A simple method for producing the compounds shown in Table 1 used in the composition of the present invention is as shown in the following synthesis example.

These production methods are merely examples, and production is also possible by methods other than those described below; however, the present invention is not limited in any way by these production methods.
Synthesis of compound 61) Add 183r of thiodiethanol to a 300d four-bottle flask.
r(].5 mol) was collected, 1.5 rr of methyl p-toluenesulfonate was added as a catalyst, and the temperature was raised under a nitrogen stream.

Reflux began at around 155°C, but as the water produced azeotroped, the temperature dropped and reached about 125°C after 30 minutes.

After continuing the reaction for another 2 hours, the pressure was reduced to remove the produced water. 150-160 while still under reduced pressure
After completely removing produced water and unreacted substances with water C, 0.6 tr of calcium hydroxide was added, stirred at 120° C. for 30 minutes to treat the catalyst, and stirred at the same temperature under reduced pressure for 30 minutes. Thereafter, the product was purified by filtration to obtain 151rr of a transparent pale yellow liquid that was highly viscous when heated. 0HV=50.9 Average degree of polymerization n=
20.9 Synthesis Example 2 (Synthesis of compound of waterfall 2) 500? 156 2-mercaptoethanol in a reaction vessel
Vr (2.0 mol), p-toluenesulfonic acid 1.5f
When 200 g of toluene and 200 g of toluene were collected and reacted for 5 hours at toluene reflux temperature under a nitrogen atmosphere, the product became insoluble in the reaction solution and formed a slurry, and the distilled water 29 g
I got r.

After cooling, the product was purified by filtration and washed with methanol to obtain 114rr of white powder. SH content: 2.65% Average degree of polymerization: n=20.4 It was confirmed from the infrared absorption spectrum that the product was the desired product.

Synthesis Example 3 (Synthesis of compound of ./F6ll) 399r of 2-mercaptoethanol (0.5
mol), 130 yr of octanol (].0 mol), and 150 fr of xylene were collected, 1.7 rr of methyl p-toluenesulfonate was added as a catalyst, and the mixture was reacted for about 10 hours at the xylene reflux temperature under a nitrogen stream, producing 8 mol of water. .5C
I got c.

The reaction product became an insoluble substance in the solution and formed a slurry. After cooling, the product was filtered and washed with methanol to obtain white powder 299r. SH content: 2.51% Average degree of polymerization: n=19.7 It was confirmed from the infrared absorption spectrum that the product was the desired product.

Synthesis Example 4 (Synthesis of Compound 21) 10% of the compound obtained in Synthesis Example 1 was placed in a 20011Z reaction vessel.
0fr (0.0455 mol) and octylic acid chloride 14.8Vr (0.091 mol) were collected and heated at 100°C.
It reacted for 1 hour.

Subsequently, impurities were distilled off for 30 minutes under reduced pressure of about 501 uHr to obtain a viscous pale yellow liquid. Yield: 111fr1 It was confirmed from the infrared absorption spectrum that the product was the desired product.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 In order to examine the excellent stabilizing effect of the compound of the present invention, samples were prepared by calendering and hot pressing according to the following formulation, and were tested for thermal stability using a heat aging tester at 175°C. Transparency and initial colorability were measured by hot pressing, and the results are shown in Table 2 below.

Regarding the initial coloration, the degree of yellowness was determined and compared using a solder colorimeter as shown in the formula below.

55' Transparency is also divided into six levels from 1 to 6, with 1 indicating almost transparent and 6 indicating almost opaque.

Example 2 Next, in order to examine the effects of the resin composition according to the present invention and Ca-Zn soap, a test was conducted by repeating the same operation as in Example 1 using the following formulation.

The results are shown in the following Table 3. Example 3 In order to see the effect of the compound according to the present invention in a hard formulation in which no plasticizer was used in the resin, a test was conducted by repeating the same operation as in Example 1 with the following formulation. Ivy.

The results are shown in Table 4. <Formulation> Example 4 In order to examine the stabilizing effect on the polyvinyl chloride-ABC resin blend product according to the present invention, samples were prepared using the following formulation in the same manner as in Example 1, and the results were summarized as follows. It is shown in Table 5.

Example 5 In order to examine the effect of adding other additives to the resin composition according to the present invention in combination, the same test as in Example 1 was conducted using the following formulation.

The results are shown in Table 6 below. Example 6 Next, in order to examine the stabilizing effect of the resin composition according to the present invention on acrylonitrile-butadiene-styrene copolymer (ABS resin), samples with a thickness of 21 nm were prepared using a kneading roll using the following formulation. 210℃, 50kg/
The color of the material was measured after Cl, IO minutes.

Note that the deterioration of ABS resin due to heat is accompanied by a change in color tone from white to light yellow, yellow, dark yellow, and brown in sequence, regardless of the presence or absence of a stabilizer.

In this example, this was divided into 10 stages and compared.
That is, 1 represents white and 10 represents brown. The test results are shown in Table 7 below. Example 7 The following formulation Z. Samples were prepared from the above, and the thermal stability and initial coloring properties were measured in a gear oven at 190°C, and the results are shown in Table 8.

Example 8 In order to see the effect when the compound according to the present invention is used in polypropylene resin, a composition having the following formulation was prepared at 180%
Knead in a roll mill for 5 minutes at
A sheet of 1.0 mm was prepared by compression molding at 80° C. for 5 minutes.

This sheet was used as a 10×20 mm test piece and was subjected to a heating test at a temperature of 160° C. in an oven capable of stirring air. The results are shown in Table 9. Incidentally, 10 test pieces were used for the same sample, and the time when 5 or more pieces became discolored and brittle was defined as the deterioration start time.

Example 9 A mill test was conducted on a composition containing the compound of the present invention according to the following formulation, and the adhesion time and decomposition time were measured, and the results are shown in Table 10 below.

Claims (1)

[Scope of Claims] 1. A synthetic resin composition stabilized by containing at least one compound represented by the following general formula (I) as a stabilizer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the above formula, R_1 and R_2 each represent a hydrogen atom, alkyl, aryl, hydroxycarbonylalkyl, arylalkyl, or acyl group. R_3 and R_4 each represent a hydrogen atom, an alkyl group, or an aryl group. X_1 and X_2 each represent a sulfur atom or an oxygen atom, and the ratio of sulfur atom/oxygen atom in one molecule is 1/2 to
The range is 80. n represents a number from 5 to 80. (In addition, if there are the same symbols in one molecule, they may be the same or different.)]